Dicops containing acetylenic substituents

ABSTRACT

An activator for olefin polymerization catalysts is disclosed. One aspect of the activator is that it comprises a group-13 central atom connected to at least one fluorinated aryl ring that is itself substituted with a silyl acetylenic group. Some embodiments employ a neutral activator and others employ the activator as an anion coupled with a ligand-abstracting cation. These activators are discrete molecules.

RELATED APPLICATIONS

[0001] This application claims priority benefit from U.S. ProvisionalApplication Serial No. 60/336,103, filed 2 Nov. 2001.

FIELD

[0002] This invention relates to polymerization cocatalyst compoundscontaining weakly coordinating Group-13-element anions and to thepreparation of olefin polymers using ionic catalyst systems based onorganometallic transition-metal cationic compounds stabilized by theseanions.

BACKGROUND

[0003] The term “noncoordinating anion” (NCA) is now acceptedterminology in the field of olefin and vinyl molecule, coordination,insertion, and carbocationic polymerization. See, for example, EP 0 277003, EP 0 277 004, U.S. Pat. No. 5,198,401, U.S. Pat. No. 5,278,119, andBaird, Michael C., et al, J. Am. Chem. Soc. 1994, 116, 6435-6436. Thenoncoordinating anions are described to function as electronicstabilizing cocatalysts, or counterions, for essentially active,cationic metallocene polymerization catalysts. The term noncoordinatinganion applies both to truly noncoordinating anions and to coordinatinganions that are labile enough to undergo replacement by olefinically oracetylenically unsaturated molecules at the insertion site. Thesenoncoordinating anions can be effectively introduced into apolymerization medium as Bronsted acid salts containing charge-balancingcountercations, as ionic cocatalyst compounds, or mixed with anorganometallic catalyst before adding it to the polymerization medium.See also, the review articles by S. H. Strauss, “The Search for Largerand More Weakly Coordinating Anions,” Chem. Rev., 93, 927-942 (1993).

[0004] U.S. Pat. No. 5,502,017, to Marks et al., addresses ionicmetallocene polymerization catalysts for olefin polymerizationcontaining a weakly coordinating anion comprising boron substituted withhalogenated aryl substituents preferably containing silylalkylsubstitution, such as a t-butyldimethyl-silyl substitution. Marks et al.disclose the weakly coordinating anion as the cocatalyst. The silylalkylsubstitution is said to increase the solubility and thermal stability ofthe resulting metallocene salts. Examples 3-5 describe synthesis of andpolymerization with the cocatalyst compound triphenylcarbenium tetrakis(4-dimethyl-t-butylsilyl-2,3,5,6-tetrafluorophenyl) borate.

[0005] Leon A. Hagelee and Roland Köster published “Boron CompoundsXLIV¹, The influence of silicon on the formation of(Z/E)-tetrasubstituted ethylenes via 1-alkynylborates; Syn. React.Inorg. Metal-Org. Chem., 7(1), 53-67 (1977). This reference reports onNMR studies of borates that incorporate trimethyl silyl groups.

[0006] Wrackmeyer, et al., published “1,6-Dihydro-1,6-disilapentalenederivatives by 1,1-organoboration of triynes”. The triynesR¹C≡—SiMe₂—C≡C—SiMe₂—C≡CR¹ [R¹=H, SiMe₃, SnMe₃] were prepared, and theirreactivity towards triorganoboranes R₃B 6 [R=Et (a), CH₂Ph (b), Ph c,2-thienyl (d)] was studied. The products were characterised by their¹H-, ¹¹B-, ¹³C-, ²⁹Si- and ¹¹⁹Sn-NMR data.

[0007] Yamaguchi, et al., published “Tridurylboranes Extended by ThreeArylethynyl Groups as a New Family of Boron-Based π-Electron Systems”. Aseries of tris(phenylethynylduryl)boranes (R—C₆H₄—C≡C-duryl)₃B withvarious substituents R have been prepared as air-stable solids owing tothe steric protection of the boron atom by the three bulky duryl groups.These compounds show unique photophysical properties.

[0008] Imamoto, et al., published “Syntheses and Properties ofTrifluoromethanesulfonyloxy Derivatives ofTricyclohexylphosphine-Borane”. Syntheses, structural characterizations,and reactions oftricyclohexylphosphine-trifluoromethanesulfonyloxyborane andtricyclohexylphosphine-bis(trifluoromethanesulfonyloxy)-borane aredescribed.

[0009] In view of the above, there is a continuing need for olefinpolymerization activators both to improve the industrial economics ofsolution polymerization and to provide alternative activating compoundsfor ionic, olefin polymerization catalyst systems.

SUMMARY

[0010] The invention provides cocatalyst compounds that can be combinedwith catalyst precursor compounds to form active catalysts for olefininsertion, coordination, or carbocationic polymerization, as well ascatalyst systems containing such cocatalyst compounds. (For purposes ofthis document, “cocatalyst compound” is interchangeable with “cocatalystactivator compound” and “activator”). Olefin polymerization can proceedby catalyst formation followed by, or in situ catalyst formationessentially concurrent with, contacting the catalyst with appropriatemolecules: those having accessible, olefinic or acetylenic unsaturationor having olefinic unsaturation capable of cationic polymerization. Moregenerally, an appropriate olefin is one that is polymerizable by acatalyst system that uses the invention cocatalyst compounds. Thecatalysts according to the invention are suitable for preparing polymersand copolymers from olefinically and acetylenically unsaturatedmolecules.

[0011] Some invention embodiments select the cocatalyst to be neutralwith three fluoroaryl ligands, while others select the cocatalyst to beionic with four fluoroaryl ligands. Some embodiments select the arylligand (otherwise known as a ring assembly) so that it comprises atleast one fluorine group.

[0012] When neutral, the cocatalyst comprises a Group-13 element boundto fluoroaryl ligands in which at least one fluoroaryl ligand issubstituted with at least one acetylenic group: (BULKY-CC-). BULKYrepresents a group that is bulky enough to kinetically orthermodynamically impede reaction of the acetlylenic group with theactivated metallocene catalyst. The neutral cocatalyst is itself theligand abstracting moiety. Upon catalyst activation, the neutralcocatalyst becomes an NCA. In more specific embodiments, at lest onearyl ligand is substituted with at least one fluorine atom (i.e. fluorosubstituted).

[0013] When ionic, the cocatalyst contains a cationic,ligand-abstracting moiety (an activating cation) and an NCA moietycomprising a Group-13 element bound to aryl ligands in which at leastone aryl ligand is substituted with at least one acetylenic group:(BULKY-CC-).

[0014] Some embodiments select a triispropylsilylacetylenic substitutionon each aryl ligand. Some embodiments select the Group-13 element to beboron. Some embodiments select the aryl ligands so that, other thanacetylenic groups, the aryl ligand or ring assembly is perfluorinated.

[0015] The ligand-abstracting moiety can abstract an alkyl group from,or break a carbon-metal bond in, an organometallic compound (i.e., thecatalyst precursor) upon contact with that compound. This process leavesa cationic catalyst, a neutral compound, and an NCA.

[0016] This invention relates to a composition of matter that containsan anionic central core wherein the anionic central core comprises aGroup-13 atom. This group-13 atom is connected to four ring assemblieswherein at least one ring assembly comprises an acetylene moiety.

[0017] This invention also relates to a composition of matter thatcontains a nuetral central core comprising a Group-13 atom. This atom isconnected to three ring assemblies wherein at least one ring assemblycomprises an acetylene moiety.

[0018] In addition, this invention relates to methods for using thesecompositions and to products produced using them.

DETAILED DESCRIPTION

[0019] Catalyst system encompasses a catalyst precursor/activator pair.When catalyst system is used to describe such a pair before activation,it means the un-activated catalyst together with the activator. Whencatalyst system is used to describe such a pair after activation, itmeans the activated catalyst and the NCA or other charge-balancingmoiety. In some cases, catalyst refers to the activated catalyst.

[0020] One aspect of this invention is an NCA comprising an acetylenesubstituent, as shown in the following formula.

[0021] The filled circle represents a bulky group that is large enoughto impede or slow down access by the active site of the metallocene tothe olefinic unsaturation of the acetylenic group. A more specificrepresentation is shown below.

[0022] In this representation, R₃Si represents the bulky group. Thus,the acetylene substitution comprises a bulky group and an acetylenicgroup. Si is silicon. Each R is an organic radical and can be the sameor different. At least one R is selected from methyl, ethyl, n-propyl,i-propyl, n-butyl, s-butyl, t-butyl, 1-pentyl, 1-methylbut-1-yl,2-methylbut-1-yl, 3-methylbut-1-yl, 2-pentyl, 3-pentyl,1,1-dimethylprop-1-yl, 1,2-dimethylprop-1-yl, and 2,2-dimethylprop-1-yl.As with the isomers of the propyl, butyl, and pentyl radicals, R canalso be selected from the isomers of the hexyl, heptyl, and octylradicals. Exemplary silyl groups include the followingOctadecyldimethylsilyl, (3-cyanopropyl) dimethylsilyl,(pentafluorophenyl)dimethylsilyl, (3-chloropropyl)dimethylsilyl,allyldimethylsilyl, butyldimethylsilyl, (chloromethyl)dimethylsil,decyl-dimethyl-silyl, diisopropylsilyl, diisopropyloctylsilyl,dimethyl(3,3,3-trifluoropropyl)silyl,dimethyl(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silyl, dimethyldodecylsilyl,dimethylisopropylsilyl, dimethylphenylsilyl, dimethyl-propyl-silyl,dimethyl-thexylsilyl, diphenyl-methylsilyl, methyl-phenyl-silyl,methyl-phenyl-vinylsilyl, Octadecyldimethylsilyl, octyldimethylsilyl,tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl,triethylsilyl, triisopropylsilyl, trimethylsilyl, triphenylsilyl,vinyldimethylsilyl, and dimethyl-thexylsilyl. Whatever the actualselection of the trialkyl silyl group it must function as a bulky group.Alternatively, suitable bulky groups need not contain silicon. And theyneed not contain carbon.

[0023] To define nomenclature, the structure of the 2-pentyl radical isshown below. This radical can also be called the 1-methylbut-1-ylradical. The connection to Si is shown.

[0024] The isopropylsilylacetylenic group has the formula shown below.It can be more formally called the 2-(triisopropylsilyl)ethynyl orethyn-1-yl radical.

[0025] One aspect of this invention is an NCA comprising the acetylenicgroups discussed above connected to an aryl group. The resultingassembly then ligates or connects to a Group-13 element (Group-13elements are sometimes referred to as triels and abbreviated as Tr).Some embodiments select the triel or Group-13 element to be B or Al.Some embodiments select the aryl group to be fluorinated orperfluorinated. Several exemplary NCAs are shown below.

[0026] tetrakis{para-[2-(triisopropylsilyl)acetyl]tetrafluorophenyl}borate, forpurposes of this disclosure, the previous term is interchangeable withtetrakis{4-[2-(triisopropylsilyl)ethynyl]tetrafluorophenyl}borate

[0027] tris {pentafluorophenyl}{para-[2-(triisopropylsilyl)acetyl]}tetrafluorophenyl}borate. For purposes of this disclosure, the previousterm is interchangeable with tris{pentafluorophenyl}{4-[2-(triisopropylsilyl)ethynyl]-tetrafluorophenyl}borate.

[0028] tris {4-[2-(triisopropylsilyl)ethynyl]tetrafluorophenyl}{3-[2-(triisopropylsilyl)ethynyl]tetrafluorophenyl} borate

[0029] The NCAs as shown above have the ethynic or acetylenic portion ofthe acetylenic group directly connected to the fluoroaryl ligand.

[0030] The ligands around the Group-13 atom serve to stabilize the ion'scharge. Furthermore, the ligands control the degree of contact betweenthe catalyst and cocatalyst. With appropriate NCA, these two effectscombine to diminish the ionic attraction between the catalyst andcocatalyst. Alternatively, the NCA can be an assembly in which theanionic charge spreads out over the molecule making the charge morediffuse. After catalyst activation, the cocatalyst should either becompletely non-coordinating or coordinate weakly enough so that theanion does not substantially impede the monomer's access to thecatalyst.

[0031] Phenyl, biphenyl, naphthyl, indenyl, anthracyl, fluorenyl,azulenyl, phenanthrenyl, and pyrenyl are suitable aryl radicals. Someembodiments select phenyl, biphenyl, or naphthyl as the aryl radicals.Exemplary ArF ligands and ArF substituents useful in this inventionspecifically include the fluorinated species of these aryl radicals.Perfluorinated aryl groups also function and include substituted ArFgroups having substituents in addition to fluorine, such as fluorinatedhydrocarbyl groups. The disclosures of U.S. Pat. Nos. 5,198,401,5,296,433, 5,278,119, 5,447,895, 5,688,634, 5,895,771, WO 93/02099, WO97/29845, WO 99/43717, WO 99/42467 and copending U.S. application Ser.No. 09/261,627, filed 3 Mar. 1999, and its equivalent WO 99/45042 teachsuitable ArF groups. Some embodiments replace at least one-third of thehydrogen atoms connected to aromatic ligands with fluorine; someembodiments select perfluorinated aryl ligands. Perfluorinated meansthat each aryl hydrogen atom is substituted with fluorine or fluorcarbylsubstituents, e.g., trifluoromethyl, pentafluoroethyl,heptafluoro-isopropyl, tris(trifluoromethyl)silyltetrafluoroethyl, andbis(trifluoroethyl) (heptafluoropropyl)silyltetrafluoroethyl.

[0032] The goal of fluorination is to remove abstractable hydrogen fromthe NCA. Therefore, any ligand choice or substitution pattern thatminimizes the number of abstractable hydrogen is useful in thisinvention's practice. Thus, suitable ligand choices and substitutionpatterns will depend somewhat on the selected catalyst. Not all hydrogensubstituents must be fluorine-replaced as long as the remaining hydrogensubstituents are substantially non-abstractable by the specific catalystof the catalyst system. Substantially non-abstractable means that thehydrogen may be extractable but at levels low enough so that the degreeof chain termination and catalyst poisoning remains below that which iscommercially reasonable. Some embodiments target lesser levels ofabstractability. Cocatalyst activators can effectively activatecatalysts for solution, bulk, slurry, and gas phase polymerizationprocesses.

[0033] Cation counterparts for invention noncoordinating anion saltsinclude those known in the art for NCAs. Various cation classes includenitrogen-containing cations such as in the anilinium and ammonium saltsof U.S. Pat. No. 5,198,401 and WO 97/35893; the carbenium, oxonium, orsulfonium cations of U.S. Pat. No. 5,387,568; metal cations, e.g., Ag⁺;the silylium cations of WO 96/08519; and those of the hydrated, Group-1or -2 metal cations of WO 97/22635.

[0034] Additionally, invention NCAs can come from neutral Lewis acidscomprising a Group-13 metal or metalloid center and from one to threehalogenated aryl ligands as described above for the invention.Complementary ligands are selected from those known in the art fornoncoordinating anions. Thus some cocatalyst embodiments are neutral andbecome anionic during the activation process. Two such examples areshown below.

tris {para-[2-(triisopropylsilyl)acetyl]-tetrafluorophenyl}borane ortris{4-[2-(triisopropylsilyl)ethynyl]tetrafluorophenyl}borane

[0035]

bis{4-[2-(triisopropylsilyl)ethynyl]tetrafluorophenyl}{3-[2-(triisopropylsilyl)ethynyl]tetrafluorophenyl}borane

[0036]

bis{pentafluorophenyl}{para-[2-(triisopropylsilyl)acetyl]}tetrafluorhenyl}boraneorbis{pentafluorophenyl}{4-[2-(triisopropylsilyl)ethynyltetrafluorophenyl}borane

[0037] In operation, an anionic cocatalyst reacts with the catalystprecursor leaving an activated cationic catalyst and a weaklycoordinating anion. Before activation, the cocatalyst contains a cation.Activation occurs when that cation either abstracts a hydride, alkyl, orsubstituted alkyl ligand, Q, from the catalyst precursor or cleaves ametal-organic bond in the precursor.

[0038] Activation transforms the cation of the cocatalyst into a neutralmolecule; the non-coordinating anion remains anionic. Activation alsotransforms the neutral catalyst precursor into a cationic catalyst,typically by abstracting a hydride or anionic alkyl, which combines withthe proton from the cocatalyst.

[0039] The acetylenic-substituted activators or cocatalysts may beprepared as follows.

[0040] i. Sonogashira conditions. ii BuLi, −78 deg C., diethylether assolvent. iii ¼ BCl₃. iv. 4-tBu-DMAHCl, methylene chloride as solvent, 25deg C.

[0041] Catalyst Precursor Compounds

[0042] When neutral cocatalysts are employed, the activation process isbelieved to proceed somewhat differently. The neutral cocatalyst itselfabstracts a ligand from the catalyst precursor becoming anionic in theprocess. After activation, the activated cationic catalyst is chargedbalanced by the NCA. In the case of a neutral cocatalyst, the NCA isfrequently the reaction product of the cocatalyst and the abstractedligand.

[0043] Suitable catalyst precursor compounds for use in this inventioninclude the known organometallic, transition metal compounds useful fortraditional Ziegler-Natta polymerization, particularly the metallocenesknown to be useful in polymerization. The catalyst precursor must besusceptible to activation by invention cocatalysts. Useful catalystprecursors include Group-3-10 transition metal compounds in which atleast one metal ligand can be abstracted by the cocatalyst.Particularly, those abstractable ligands include hydride, hydrocarbyl,hydrocarbylsilyl, and their lower-alkyl-substituted (C₁-C₁₀)derivatives. Examples include hydride, methyl, benzyl,dimethyl-butadiene, etc. Abstractable ligands and transition metalcompounds comprising them include those metallocenes described in, forexample, U.S. Pat. No. 5,198,401 and WO 92/00333. Syntheses of thesecompounds are well known from the published literature. Additionally, inthose cases where the metal ligands include labile halogen, amido, oralkoxy ligands (for example, biscyclopentadienyl zirconium dichloride),which may not allow for ready abstraction by invention's cocatalysts,the ligands can be replaced with abstractable ones. This replacementuses known routes such as alkylation with lithium or aluminum hydrides,alkyls, alkylalumoxanes, Grignard reagents, etc. See also EP 0 500 944and EP 0 570 982 for the reaction of organoaluminum compounds withdihalo-substituted metallocenes prior to catalyst activation.

[0044] Additional descriptions of metallocene compounds with, or thatcan be alkylated to contain, at least one ligand abstractable to formcatalytically active transition-metal cations appear in the patentliterature. (E.g., EP-A-0 129 368, U.S. Pat. Nos. 4,871,705, 4,937,299,5,324,800, 5,470,993, 5,491,246, 5,512,693, EP-A-0 418 044, EP-A-0 591756, WO-A-92/00333, WO-A-94/01471 and WO 97/22635.) Such metallocenescan be described as mono- or biscyclopentadienyl-substituted Group-3,-4, -5, or -6 transition metals. The transition metal ligands maythemselves be substituted with one or more groups, and the ligands maybridge to each other or bridge through a heteroatom to the transitionmetal. The size and constituency of the ligands and bridging elementsshould be chosen in the literature-described manner to enhance activityand to select desired characteristics. Embodiments in which thecyclopentadienyl rings (including substituted, cyclopentadienyl-based,fused-ring systems, such as indenyl, fluorenyl, azulenyl, or theirsubstituted analogs), when bridged to each other, are lower-alkylsubstituted (C₁-C₆) in the 2 position (with or without a similar4-position substituent in the fused ring are useful). Thecyclopentadienyl rings may additionally comprise alkyl, cycloalkyl,aryl, alkylaryl, and arylalkyl substituents, the latter as linear,branched, or cyclic structures including multi-ring structures, forexample, those of U.S. Pat. Nos. 5,278,264 and 5,304,614. In someembodiments, such substituents should each have essentially hydrocarbylcharacteristics and will typically contain up to 30 carbon atoms, butmay contain heteroatoms, such as 1 to 5 non-hydrogen or non-carbonatoms, e.g., N, S, O, P, Ge, B and Si.

[0045] Invention activators are useful with essentially all knownmetallocene catalyst that are suitable for preparing polyolefins fromC₂-C₁₀ α-olefin monomer or mixtures of monomers, see again WO-A-92/00333and U.S. Pat. Nos. 5,001,205, 5,198,401, 5,324,800, 5,304,614 and5,308,816, for specific listings. Criteria for selecting suitablemetallocene catalysts for making polyethylene and polypropylene are wellknown in the art, in both patent and academic literature, see forexample Journal of Organometallic Chemistry 369, 359-370 (1989).Likewise, methods for preparing these metallocenes are also known.Typically, the catalysts are stereorigid, asymmetric, chiral, orbridged-chiral metallocenes. See, for example, U.S. Pat. No. 4,892,851,U.S. Pat. No. 5,017,714, U.S. Pat. No. 5,296,434, U.S. Pat. No.5,278,264, WO-A-(PCT/US92/10066) WO-A-93/19103, EP-A2-0 577 581, EP-A1-0578 838, and academic literature “The Influence of Aromatic Substituentson the Polymerization Behavior of Bridged Zirconocene Catalysts”,Spaleck, W., et al, Organometallics 1994, 13, 954-963, and“ansa-Zirconocene Polymerization Catalysts with Annelated RingLigands-Effects on Catalytic Activity and Polymer Chain Lengths”,Brinzinger, H., et al, Organometallics 1994, 13, 964-970, and documentsreferred to therein. Though many of these references deal withalumoxane-activated catalyst systems, analogous metallocenes can beactivated with this invention's cocatalysts. In catalyst systems lackingabstractable ligands, at least one non-abstractable ligand must first bereplaced with an abstractable one. Replacement by alkylation, asdescribed above, is one example. Additionally, the metallocenes shouldcontain a group into which an ethylene or α-olefin group, —C═C—, mayinsert, for example, hydride, alkyl, alkenyl, or silyl. See additionaldescription in G. G. Hlatky, “Metallocene catalysts for olefinpolymerization Annual review of 1996”, Coordination Chemistry Reviews,181, 243-296 (Elsevier Science, 1999).

[0046] Representative metallocene compounds can have the formula:

L_(A)L_(B)L_(Ci)MDE

[0047] where M is a Group-3-10 metal; L_(A) is a substituted orunsubstituted, cyclopentadienyl or heterocyclopentadienyl ligandconnected to M; and L_(B) is a ligand as defined for L_(A), or is J, aheteroatom ligand connected to M. L_(A) and L_(B) may connect to eachother through a Group-13-16-element-containing bridge. L_(Ci) is anoptional, neutral, non-oxidizing ligand connected to M (i equals 0 to3); and D and E are the same or different labile ligands, optionallybridged to each other, L_(A), or L_(B). Each of D and E are connected toM. Some embodiments select M to be a member of the Group-3-6 transitionmetals. Other embodiments select M to be a Group-4 transition metal.Some embodiments select M to be Ti, Zr, or Hf.

[0048] D and E's identity is functionally constrained. The firstconstraint is that upon activation, either the D-M or the E-M connectionmust break. D and E should be chosen to facilitate this. Anotherconstraint is that a polymerizable molecule must be able to insertbetween M and whichever of D or E remains.

[0049] Cyclopentadienyl and heterocyclopentadienyl ligands encompassfused-ring systems including but not limited to indenyl and fluorenylradicals. Also, the use of heteroatom-containing rings or fused rings,where a non-carbon, Group-13, -14, -15, or -16 atom replaces a ringcarbon is within the term “cyclopentadienyl” for this specification.See, for example, the background and illustrations of WO 98/37106,having priority with U.S. Ser. No. 08/999,214, filed Dec. 29, 1997, andWO 98/41530, having priority with U.S. Ser. No. 09/042,378, filed Mar.13, 1998. Substituted cyclopentadienyl structures are structures inwhich one or more hydrogen atoms are replaced by a hydrocarbyl,hydrocarbylsilyl, or similar heteroatom-containing structure.Hydrocarbyl structures specifically include C₁-C₃₀ linear, branched, andcyclic alkyl, and aromatic fused and pendant rings. These rings may alsobe substituted with ring structures.

[0050] Catalyst precursors also include the mono- andbiscyclopentadienyl compounds such as those listed and described in U.S.Pat. Nos. 5,017,714, 5,324,800, WO 92/00333 and EP-A-0 591 756.

[0051] Bis amide catalyst precursors are useful with inventioncocatalysts. Bisamide catalyst precursors are those precursors that havethe following formula:

[0052] M is Ti, Zr, or Hf. R are the same or different alkyls, aryls,substituted alkyl, or substituted aryls. X are the same or differentalkyls, aryls, or halides.

[0053] Substituted alkyl and aryls can be alkyl-, aryl-, andhalo-substituted. When X is a halide, the bisamide catalyst precursormust first be chemically modified to transform X into an abstractableligand. This can be done by alkylation, for example.

[0054] Pyridine bisamide catalyst precursors are also useful withinvention cocatalysts. Pyridine bisamide catalyst precursors are thoseprecursors that have the following formula:

[0055] M is Ti, Zr, or Hf. R are the same or different alkyls, aryls,substituted alkyl, or substituted aryls. X are the same or differentalkyls, aryls, or halides.

[0056] Substituted alkyl and aryls can be alkyl-, aryl-, andhalo-substituted.

[0057] When X is a halide, the pyridine bisamide catalyst precursor mustfirst be chemically modified to transform X into an abstractable ligand.This can be done by alkylation, for example.

[0058] Amine bisamide catalyst precursors are also useful with inventioncocatalysts. Amine bisamide catalyst precursors are those precursorsthat have the following formula:

[0059] M is Ti, Zr, or Hf. R and R′ are the same or different alkyls,aryls, substituted alkyl, or substituted aryls. X are the same ordifferent alkyls, aryls, or halides.

[0060] Substituted alkyl and aryls can be alkyl-, aryl-, andhalo-substituted. When X is a halide, the amine bisamide catalystprecursor must first be chemically modified to transform X into anabstractable ligand. This can be done by alkylation, for example.

[0061] Additional exemplary metallocene-type catalysts include thosemetallocene compounds represented by the formula:

[0062] In the above structure, M¹ is selected from titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten.

[0063] R¹ and R² are identical or different and are selected fromhydrogen atoms, C₁-C₁₀ alkyl groups, C₁-C₁₀ alkoxy groups, C₆-C₁₀ arylgroups, C₆-C₁₀ aryloxy groups, C₂-C₁₀ alkenyl groups, C₂-C₄₀ alkenylgroups, C₇-C₄₀ arylalkyl groups, C₇-C₄₀ alkylaryl groups, C₈-C₄₀arylalkenyl groups, OH groups or halogen atoms; or conjugated dienesthat are optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl)silyl groups or hydrocarbyl,tri(hydrocarbyl)silylhydrocarbyl groups. The conjugated diene cancontain up to 30 atoms not counting hydrogen.

[0064] R³ are the same or different and are selected from hydrogen atom,halogen atoms, C₁-C₁₀ halogenated or unhalogenated alkyl groups, C₆-C₁₀halogenated or unhalogenated aryl groups, C₂-C₁₀ halogenated orunhalogenated alkenyl groups, C₇-C₄₀ halogenated or unhalogenatedarylalkyl groups, C₇-C₄₀ halogenated or unhalogenated alkylaryl groups,C₈-C₄₀ halogenated or unhalogenated arylalkenyl groups, —NR′₂, —SR′,—OR′, —OSiR′₃ or —PR′₂ radicals in which R′ is one of a halogen atom, aC₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group.

[0065] R⁴ to R⁷ are the same or different and are hydrogen, as definedfor R³ or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings.

[0066] R¹³ is selected from

[0067] —B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—,—CO—, —P(R¹⁴)— —P(O)(R¹⁴)—, —B(NR¹⁴R¹⁵)— and —B[N(SiR¹⁴R¹⁵R¹⁶)₂]—. R¹⁴,R¹⁵ and R¹⁶ are each independently selected from hydrogen, halogen,C₁-C₂₀ alkyl groups, C₆-C₃₀ aryl groups, C₁-C₂₀ alkoxy groups, C₂-C₂₀alkenyl groups, C₇-C₄₀ arylalkyl groups, C₈-C₄₀ arylalkenyl groups andC₇-C₄₀ alkylaryl groups, or R¹⁴ and R¹⁵, together with the atom(s)connecting them, form a ring; and M³ is selected from carbon, silicon,germanium and tin. Alternatively, R¹³ is represented by the formula:

[0068] wherein R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings; M² is carbon, silicon,germanium, or tin.

[0069] R⁸, R⁹, R¹⁰ R¹¹ and R¹² are identical or different and have themeanings stated for R⁴ to R⁷.

[0070] Non-limiting representative catalyst precursor compounds includethe following compounds: pentamethylcyclopentadienyltitaniumisopropoxide; pentamethylcyclopentadienyltribenzyl titanium;dimethylsilyltetramethyl-cyclopentadienyl-t-butylamido titaniumdichloride; pentamethylcyclopentadienyl titanium trimethyl;dimethylsilyltetramethylcyclopentadienyl-t-butylamido zirconiumdimethyl; dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdihydride; dimethylsilyltetramethylcyclopentadienyl-dodecylamido hafniumdimethyl; unbridged biscyclopentadienyl compounds such as bis(1-methyl;3-butylcyclopentadienyl)zirconium dimethyl;(pentamethylcyclopentadienyl-cyclopentadienyl)zirconium dimethyl;(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdimethyl; bridged bis-cyclopentadienyl;dimethylsilylbis(tetrahydroindenyl)zirconium dichloride;silacyclobutyl(tetramethylcyclopentadienyl)(n-propyl-cyclopentadienyl)zirconiumdimethyl; dimethylsilyl (bisindenyl)zirconium dichloride;dimethylsily(bisindenyl)hafnium dimethyl;dimethylsilylbis(2-methylbenzindenyl)zirconium dichloride;dimethylsilylbis(2-methylbenzindenyl)zirconium dimethyl; andfluorenyl-ligand-containing compounds; e.g.;diphenylmethyl(fluorenyl)(cyclopentadienyl)zirconium dimethyl;tetrabenzyl zirconium; tetrabis(trimethyl-silylmethyl)zirconium;oxotris(trimethlsilylmethyl)vanadium; tetrabenzyl hafnium; tetrabenzyltitanium; bis(hexamethyldisilazido)dimethyltitanium;tris(trimethylsilylmethyl)niobium dichloride;tris(trimethylsilylmethyl)tantalum dichloride;(benzylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(benzylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(benzylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(benzylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(benzylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(benzylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(dimethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(dimethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(dimethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(dimethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(dimethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(dimethylcyclopentadienyl)(cyclopentadienyl)-zirconium dimethyl;(diphenylmethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(diphenylmethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(diphenylmethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(diphenylmethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(diphenylmethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(diphenylmethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(ethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(ethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(ethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(ethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(ethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(ethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(ethyltetramethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(ethyltetramethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(ethyltetramethylcyclopentadienyl)(cyclopentadienyl)-titanium dihydride;(ethyltetramethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(ethyltetramethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(ethyltetramethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(indenyl)(cyclopentadienyl)hafnium dihydride;(indenyl)(cyclopentadienyl)hafnium dimethyl;(indenyl)(cyclopentadienyl)titanium dihydride;(indenyl)(cyclopentadienyl)titanium dimethyl;(indenyl)(cyclopentadienyl)zirconium dihydride;(indenyl)(cyclopentadienyl)zirconium dimethyl;(methylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(methylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(methylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(methylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(methylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(methylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(n-butylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(n-butylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(n-butylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(n-butylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(n-butylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(n-butylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(pentamethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(pentamethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(pentamethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(pentamethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(pentamethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(pentamethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(propylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(propylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(propylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(propylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(propylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(propylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(t-butylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(t-butylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(t-butylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(t-butylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(t-butylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(t-butylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(tetramethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(tetramethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(tetramethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(tetramethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(trifluoromethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(trifluoromethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(trifluoromethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(trifluoromethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(trifluoromethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(trifluoromethylcyclopentadienyl)-(cyclopentadienyl)zirconium dimethyl;(trimethylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(trimethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(trimethylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(trimethylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(trimethylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(trimethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(trimethylgermylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(trimethylgermylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(trimethylgermylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(trimethylgermylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(trimethylgermylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(trimethylgermylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(trimethylplumbylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(trimethylplumbylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(trimethylplumbylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(trimethylplumbylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(trimethylplumbylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(trimethylplumbylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(trimethylsilylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(trimethylsilylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;(trimethylsilylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(trimethylsilylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;(trimethylsilylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;(trimethylsilylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;(trimethylstannylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;(trimethylstannylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;(trimethylstannylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;[1,1′-(1,1,2,2-tetramethyldisilanylene)bis(3-methylcyclopentadienyl)]zirconium dimethyl;[1,1′-(1,1,2,2-tetramethyldisilanylene)bis(3-trimethylsilanylcyclopentadienyl)]zirconium dimethyl;[1,1′-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)]hafnium dimethyl;[1,1′-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)]titanium dimethyl;[1,1′-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)]zirconium dimethyl;[1,1′-(1,1,3,3-tetramethyldisiloxanylene)bis(4,5,6,7-tetrahydroindenyl)]hafnium dimethyl;[1,1′-(1,1,3,3-tetramethyldisiloxanylene)bis(4,5,6,7-tetrahydroindenyl)]titanium dimethyl;[1,1′-(1,1,3,3-tetramethyldisiloxanylene)bis(4,5,6,7-tetrahydroindenyl)]zirconium dimethyl;[1,1′-(1,1,4,4-tetramethyl-1,4-disilanylbutylene)bis(4,5,6,7-tetrahydroindenyl)]hafnium dimethyl;[1,1′-(1,1,4,4-tetramethyl-1,4-disilanylbutylene)bis(4,5,6,7-tetrahydroindenyl)]titanium dimethyl;[1,1′-(1,1,4,4-tetramethyl-1,4-disilanylbutylene)bis(4,5,6,7-tetrahydroindenyl)]zirconium dimethyl;[1,1′-(2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)]hafnium dimethyl;[1,1′-(2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)]titanium dimethyl;[1,1′-(2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)]zirconium dimethyl;[1,1′-dimethylsilanylenebis(3-methylcyclopentadienyl)] hafnium dimethyl;[1,1′-dimethylsilanylenebis(3-methylcyclopentadienyl)] titaniumdimethyl; [1,1′-dimethylsilanylenebis(3-methylcyclopentadienyl)]zirconium dimethyl;[1,1′-dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)]hafnium dimethyl;[1,1′-dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)]titanium dimethyl;[1,1′-dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)]zirconium dimethyl;[1,1′-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)] hafniumdimethyl; [1,1′-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)]titanium dimethyl;[1,1′-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)] zirconiumdimethyl; [1,1′-dimethylsilanylene-bis(indenyl)] hafnium dimethyl;[1,1′-dimethylsilanylene-bis(indenyl)] titanium dimethyl;[1,1′-dimethylsilanylene-bis(indenyl)] zirconium dimethyl;bis(benzylcyclopentadienyl)hafnium dihydride;bis(benzylcyclopentadienyl)hafnium dimethyl;bis(benzylcyclopentadienyl)titanium dihydride;bis(benzylcyclopentadienyl)titanium dimethyl;bis(benzylcyclopentadienyl)zirconium dihydride;bis(benzylcyclopentadienyl)zirconium dimethyl;bis(cyclohexylmethylcyclopentadienyl)hafnium dihydride;bis(cyclohexylmethylcyclopentadienyl)hafnium dimethyl;bis(cyclohexylmethylcyclopentadienyl)titanium dihydride;bis(cyclohexylmethylcyclopentadienyl)titanium dimethyl;bis(cyclohexylmethylcyclopentadienyl)zirconium dihydride;bis(cyclohexylmethylcyclopentadienyl)zirconium dimethyl;bis(cyclopentadienyl)(trimethylsilyl)(methyl)hafnium;bis(cyclopentadienyl)(trimethylsilyl)(methyl)titanium;bis(cyclopentadienyl)(trimethylsilyl)(methyl)zirconium;bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)hafnium;bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)titanium;bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)zirconium;bis(cyclopentadienyl)(trimethylsilyl)(tris(trimethylsilyl)(trimethylsilylbenzyl);bis(cyclopentadienyl)(triphenylsilyl)(methyl)hafnium;bis(cyclopentadienyl)(triphenylsilyl)(methyl)titanium;bis(cyclopentadienyl)(triphenylsilyl)(methyl)zirconium;bis(cyclopentadienyl)hafnium di(m-tolyl); bis(cyclopentadienyl)hafniumdi(p-tolyl); bis(cyclopentadienyl)hafnium dibutyl;bis(cyclopentadienyl)hafnium diethyl; bis(cyclopentadienyl)hafniumdihydride; bis(cyclopentadienyl)hafnium dimethyl;bis(cyclopentadienyl)hafnium dineopentyl; bis(cyclopentadienyl)hafniumdiphenyl; bis(cyclopentadienyl)hafnium dipropyl;bis(cyclopentadienyl)titanium di(m-tolyl); bis(cyclopentadienyl)titaniumdi(p-tolyl); bis(cyclopentadienyl)titanium dibutyl;bis(cyclopentadienyl)titanium diethyl; bis(cyclopentadienyl)titaniumdihydride; bis(cyclopentadienyl)titanium dimethyl;bis(cyclopentadienyl)titanium dineopentyl; bis(cyclopentadienyl)titaniumdiphenyl; bis(cyclopentadienyl)titanium dipropyl;bis(cyclopentadienyl)zirconium di(m-tolyl);bis(cyclopentadienyl)zirconium di(p-tolyl);bis(cyclopentadienyl)zirconium dibutyl; bis(cyclopentadienyl)zirconiumdiethyl; bis(cyclopentadienyl)zirconium dihydride;bis(cyclopentadienyl)zirconium dimethyl; bis(cyclopentadienyl)zirconiumdineopentyl; bis(cyclopentadienyl)zirconium diphenyl;bis(cyclopentadienyl)zirconium dipropyl;bis(dimethylcyclopentadienyl)hafnium dihydride;bis(dimethylcyclopentadienyl)hafnium dimethyl;bis(dimethylcyclopentadienyl)titanium dihydride;bis(dimethylcyclopentadienyl)titanium dimethyl;bis(dimethylcyclopentadienyl)zirconium dihydride;bis(dimethylcyclopentadienyl)zirconium dimethyl;bis(diphenylmethylcyclopentadienyl)hafnium dihydride;bis(diphenylmethylcyclopentadienyl)hafnium dimethyl;bis(diphenylmethylcyclopentadienyl)titanium dihydride;bis(diphenylmethylcyclopentadienyl)titanium dimethyl;bis(diphenylmethylcyclopentadienyl)zirconium dihydride;bis(diphenylmethylcyclopentadienyl)zirconium dimethyl;bis(ethylcyclopentadienyl)hafnium dimethyl;bis(ethylcyclopentadienyl)titanium dimethyl;bis(ethylcyclopentadienyl)zirconium dimethyl;bis(ethyltetramethylcyclopentadienyl)hafnium dimethyl;bis(ethyltetramethylcyclopentadienyl)titanium dimethyl;bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl;bis(ethyltetramethylcyclopentadienyl)hafnium dihydride;bis(ethyltetramethylcyclopentadienyl)titanium dihydride;bis(ethyltetramethylcyclopentadienyl)zirconium dihydride;bis(indenyl)hafnium dihydride; bis(indenyl)hafnium dimethyl;bis(indenyl)titanium dihydride; bis(indenyl)titanium dimethyl;bis(indenyl)zirconium dihydride; bis(indenyl)zirconium dimethyl;bis(methylcyclopentadienyl)hafnium dimethyl;bis(methylcyclopentadienyl)titanium dimethyl;bis(methylcyclopentadienyl)zirconium dimethyl;bis(methylcyclopentadienyl)hafnium dihydride;bis(methylcyclopentadienyl)titanium dihydride;bis(methylcyclopentadienyl)zirconium dihydride;bis(n-butylcyclopentadienyl)hafnium dimethyl;bis(n-butylcyclopentadienyl)titanium dimethyl;bis(n-butylcyclopentadienyl)zirconium dimethyl;bis(n-butylcyclopentadienyl)hafnium dihydride;bis(n-butylcyclopentadienyl)titanium dihydride;bis(n-butylcyclopentadienyl)zirconium dihydride;bis(pentamethylcyclopentadienyl)(benzyne)hafnium;bis(pentamethylcyclopentadienyl)(benzyne)titanium;bis(pentamethylcyclopentadienyl)(benzyne)zirconium;bis(pentamethylcyclopentadienyl)hafnium dimethyl;bis(pentamethylcyclopentadienyl)titanium dimethyl;bis(pentamethylcyclopentadienyl)zirconacyclopentane;bis(pentamethylcyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)hafnium (methyl)(hydride);bis(pentamethylcyclopentadienyl)hafnium (phenyl)(hydride);bis(pentamethylcyclopentadienyl)hafnium dihydride;bis(pentamethylcyclopentadienyl)titanium (methyl)(hydride);bis(pentamethylcyclopentadienyl)titanium (phenyl)(hydride);bis(pentamethylcyclopentadienyl)titanium dihydride;bis(pentamethylcyclopentadienyl)zirconacyclobutane;bis(pentamethylcyclopentadienyl)zirconium (methyl)(hydride);bis(pentamethylcyclopentadienyl)zirconium (phenyl)(hydride);bis(pentamethylcyclopentadienyl)zirconium dihydride;bis(propylcyclopentadienyl)hafnium dimethyl;bis(propylcyclopentadienyl)titanium dimethyl;bis(propylcyclopentadienyl)zirconium dimethyl;bis(propylcyclopentadienyl)hafnium dihydride;bis(propylcyclopentadienyl)titanium dihydride;bis(propylcyclopentadienyl)zirconium dihydride;bis(t-butylcyclopentadienyl)hafnium dimethyl;bis(t-butylcyclopentadienyl)titanium dimethyl;bis(t-butylcyclopentadienyl)zirconium dimethyl;bis(t-butylcyclopentadienyl)hafnium dihydride;bis(t-butylcyclopentadienyl)titanium dihydride;bis(t-butylcyclopentadienyl)zirconium dihydride;bis(tetramethylcyclopentadienyl)hafnium dihydride;bis(tetramethylcyclopentadienyl)hafnium dimethyl;bis(tetramethylcyclopentadienyl)titanium dihydride;bis(tetramethylcyclopentadienyl)titanium dimethyl;bis(tetramethylcyclopentadienyl)zirconium dihydride;bis(tetramethylcyclopentadienyl)zirconium dimethyl;bis(trifluoromethylcyclopentadienyl)hafnium dihydride;bis(trifluoromethylcyclopentadienyl)hafnium dimethyl;bis(trifluoromethylcyclopentadienyl)titanium dihydride;bis(trifluoromethylcyclopentadienyl)titanium dimethyl;bis(trifluoromethylcyclopentadienyl)zirconium dihydride;bis(trifluoromethylcyclopentadienyl)zirconium dimethyl;bis(trimethylcyclopentadienyl)hafnium dihydride;bis(trimethylcyclopentadienyl)hafnium dimethyl;bis(trimethylcyclopentadienyl)titanium dihydride;bis(trimethylcyclopentadienyl)titanium dimethyl;bis(trimethylcyclopentadienyl)zirconium dihydride;bis(trimethylcyclopentadienyl)zirconium dimethyl;bis(trimethylgermylcyclopentadienyl)hafnium dihydride;bis(trimethylgermylcyclopentadienyl)hafnium dimethyl;bis(trimethylgermylcyclopentadienyl)titanium dihydride;bis(trimethylgermylcyclopentadienyl)titanium dimethyl;bis(trimethylgermylcyclopentadienyl)zirconium dihydride;bis(trimethylgermylcyclopentadienyl)zirconium dimethyl;bis(trimethylplumbylcyclopentadienyl)hafnium dihydride;bis(trimethylplumbylcyclopentadienyl)hafnium dimethyl;bis(trimethylplumbylcyclopentadienyl)titanium dihydride;bis(trimethylplumbylcyclopentadienyl)titanium dimethyl;bis(trimethylplumbylcyclopentadienyl)zirconium dihydride;bis(trimethylplumbylcyclopentadienyl)zirconium dimethyl;bis(trimethylsilylcyclopentadienyl)hafnium dihydride;bis(trimethylsilylcyclopentadienyl)hafnium dimethyl;bis(trimethylsilylcyclopentadienyl)titanium dihydride;bis(trimethylsilylcyclopentadienyl)titanium dimethyl;bis(trimethylsilylcyclopentadienyl)zirconium dihydride;bis(trimethylsilylcyclopentadienyl)zirconium dimethyl;bis(trimethylstannylcyclopentadienyl)hafnium dihydride;bis(trimethylstannylcyclopentadienyl)titanium dihydride;bis(trimethylstannylcyclopentadienyl)zirconium dihydride; dibutylsilyl(fluorenyl)(cyclopentadienyl)hafnium dimethyl;diethylsilanediylbis-(2-methylindenyl)-zirconium diethyl;diethylsilanediylbis-(2-methylindenyl)-zirconium dimethyl;dimethylsilanediylbis-(2-ethyl-5-isopropylcyclopentadienyl)-zirconiumdimethyl; dimethylsilanediylbis-(2-ethyl-indenyl)-zirconium dimethyl;dimethylsilanediylbis-(2-isopropylindenyl)zirconium dimethyl;dimethylsilanediylbis-(2-methyl-5-ethylcyclopentadienyl)zirconiumdimethyl;dimethylsilanediylbis-(2-methyl-5-methylcyclopentadienyl)zirconiumdimethyl; dimethylsilanediylbis-(2-methylbenzindenyl)-zirconiumdimethyl; dimethylsilanediylbis-(2-methylindanyl)-zirconium dimethyl;dimethylsilanediylbis-(2-methylindenyl)-hafnium dimethyl;dimethylsilanediylbis-(2-methylindenyl)-zirconium dimethyl;dimethylsilanediylbis-(2-t-butylindenyl)zirconium dimethyl;dimethylsilyl (indenyl)(fluorenyl)hafnium dihydride; dimethylsilylbis(2-methyl-indenyl)hafnium dimethyl; dimethylsilylbis(2-propylindenyl)hafnium dimethyl; dimethylsilyl bis(4-methyl,2-phenyl-indenyl)hafnium dimethyl; dimethylsilylbis(cyclopentadienyl)hafnium dihydride; dimethylsilylbis(cyclopentadienyl)titanium dihydride; dimethylsilylbis(cyclopentadienyl)zirconium dihydride; dimethylsilylbis(indenyl)hafnium dimethyl;dimethylsilyl(methylcyclopentadienyl)(1-fluorenyl)hafnium dihydride;dimethylsilyl(methylcyclopentadienyl)(1-fluorenyl)titanium dihydride;dimethylsilyl(methylcyclopentadienyl)(1-fluorenyl)zirconium dihydride;dimethylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium dihydride;dimethylsilylbis(3-trimethylsilylcyclopentadienyl)titanium dihydride;dimethylsilylbis(3-trimethylsilylcyclopentadienyl)zirconium dihydride;dimethylsilylbis(indenyl)hafnium dimethyl;dimethylsilylbis(indenyl)titanium dimethyl;dimethylsilylbis(indenyl)zirconium dimethyl;dimethylthiobis-(2-methylindenyl)-zirconium dimethyl; dinapthylmethylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl; diphenylmethylene(2,7-di-n-butyl fluorenyl)(cyclopentadienyl)hafnium dimethyl;diphenylmethylene (2,7-di-n-butyl fluorenyl)(fluorenyl)hafnium dimethyl;diphenylmethylene (2,7-di-t-butyl fluorenyl)(cyclopentadienyl)hafniumdimethyl; diphenylmethylene (2,7-di-t-butyl fluorenyl)(fluorenyl)hafniumdimethyl; diphenylmethylene(2,7-di-t-butyl-5-methylfluorenyl)(cyclopentadienyl)hafnium dimethyl;diphenylmethylene (cyclopentadienyl)(2,7-dimethylfluorenyl)hafniumdimethyl; diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl; diphenylmethylene (indenyl)(2,7-di-t-butylfluorenyl)hafnium dibenzyl; ethylene bis(cyclopentadienyl)hafniumdihydride; ethylene bis(cyclopentadienyl)hafnium dihydride;dimethylsilyl bis(cyclopentadienyl)hafnium dihydride; ethylenebis(cyclopentadienyl)hafnium dimethyl; ethylenebis(cyclopentadienyl)titanium dihydride; ethylenebis(cyclopentadienyl)titanium dihydride; dimethylsilylbis(cyclopentadienyl)titanium dihydride; ethylenebis(cyclopentadienyl)titanium dimethyl; ethylenebis(cyclopentadienyl)zirconium dihydride; ethylenebis(cyclopentadienyl)zirconium dihydride; ethylenebis(cyclopentadienyl)zirconium dimethyl; ethylenebis(indenyl)hafniumdimethyl; ethylenebis(indenyl)titanium dimethyl;ethylenebis(indenyl)zirconium dimethyl;ethylenebis(tetrahydroindenyl)hafnium dimethyl;ethylenebis(tetrahydroindenyl)titanium dimethyl;ethylenebis(tetrahydroindenyl)zirconium dimethyl; i-propyl(cyclopentadienyl)(fluorenyl)hafnium dimethyl;isopropyl(cyclopentadienyl)(1-fluorenyl)hafnium dimethyl;isopropyl(cyclopentadienyl)(1-fluorenyl)titanium dimethyl;isopropyl(cyclopentadienyl)(1-fluorenyl)zirconium dimethyl;isopropyl(cyclopentadienyl)(1-octahydro-fluorenyl)hafnium dimethyl;isopropyl(cyclopentadienyl)(1-octahydro-fluorenyl)titanium dimethyl;isopropyl(cyclopentadienyl)(1-octahydro-fluorenyl)zirconium dimethyl;methylene (2,7-di-t-butyl fluorenyl)(fluorenyl)hafnium dimethyl;methylene (indenyl)(2,7-di-t-butyl-fluorenyl)hafnium dimethyl; methylenebis(cyclopentadienyl)hafnium dimethyl; methylenebis(cyclopentadienyl)titanium dimethyl; methylenebis(cyclopentadienyl)zirconium dimethyl; methylene bis(fluorenyl)hafniumdimethyl; methylene(cyclopentadienyl(tetramethylcyclopentadienyl)hafnium dimethyl;methylene(cyclopentadienyl (tetramethylcyclopentadienyl)titaniumdimethyl; methylene(cyclopentadienyl(tetramethylcyclopentadienyl)zirconium dimethyl;methylene(cyclopentadienyl)(1-fluorenyl)hafnium dihydride;methylene(cyclopentadienyl)(1-fluorenyl)titanium dihydride;methylene(cyclopentadienyl)(1-fluorenyl)zirconium dihydride;methylphenylmethylene bis(fluorenyl)hafnium dimethyl;bis(methylcyclopentadienyl)zirconium dimethyl;bis(ethylcyclopentadienyl)zirconium dimethyl;bis(methylcyclopentadienyl)zirconium dimethyl;bis(ethylcyclopentadienyl)zirconium dimethyl;bis(methylcyclopentadienyl)zirconium dihydride;bis(ethylcyclopentadienyl)zirconium dihydride;bis(dimethylcyclopentadienyl)zirconium dimethyl;bis(trimethylcyclopentadienyl)zirconium dimethyl;bis(tetramethylcyclopentadienyl)zirconium dimethyl;bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl;bis(indenyl)zirconium dimethyl; bis(dimethylcyclopentadienyl)zirconiumdimethyl; bis(trimethylcyclopentadienyl)zirconium dimethyl;bis(tetramethylcyclopentadienyl)zirconium dimethyl;bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl;bis(indenyl)zirconium dimethyl; bis(dimethylcyclopentadienyl)zirconiumdihydride; bis(trimethylcyclopentadienyl)zirconium dihydride;bis(ethyltetramethylcyclopentadienyl)zirconium dihydride;bis(trimethylsilylcyclopentadienyl)zirconium dimethyl;bis(trimethylsilylcyclopentadienyl)zirconium dihydride;bis(trifluoromethylcyclopentadienyl)zirconium dimethyl;bis(trifluoromethylcyclopentadienyl)zirconium dimethyl;bis(trifluoromethylcyclopentadienyl)zirconium dihydride;isopropylidene-bis(indenyl)zirconium dimethyl;isopropylidene-bis(indenyl)zirconium dimethyl;isopropylidene-bis(indenyl)zirconium dihydride;pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dimethyl;isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dimethyl;dimethylsilyl(cyclopentadienyl)(fluorenyl)zirconium dimethyl;isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dihydride,bis(cyclopentadienyl)zirconium dimethyl; bis(cyclopentadienyl)zirconiumdimethyl; bis(cyclopentadienyl)zirconium diethyl;bis(cyclopentadienyl)zirconium dipropyl; bis(cyclopentadienyl)zirconiumdiphenyl; methylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;ethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;methylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;ethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;methylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;ethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;dimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;trimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)zirconium dimethyl;tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;indenyl(cyclopentadienyl)zirconium dimethyl;dimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;trimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;bis(pentamethylcyclopentadienyl)zirconium dimethyl;ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;indenyl(cyclopentadienyl)zirconium dimethyl;dimethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;trimethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;bis(pentamethylcyclopentadienyl)zirconium dihydride;indenyl(cyclopentadienyl)zirconium dihydride;trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;bis(cyclopentadienyl)(trimethylsilyl)(methyl)zirconium;bis(cyclopentadienyl)(triphenylsilyl)(methyl)zirconium;bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)zirconium;bis(cyclopentadienyl)[bis(methylsilyl)silyl](methyl)zirconium;bis(cyclopentadienyl)(trimethylsilyl)(trimethylsilyl methyl)zirconium;bis(cyclopentadienyl)(trimethylsilyl)(benzyl)zirconium;methylene-bis(cyclopentadienyl)zirconium dimethyl;ethylene-bis(cyclopentadienyl)zirconium dimethyl;isopropylidene-bis(cyclopentadienyl)zirconium dimethyl;dimethylsilylbis(cyclopentadienyl)zirconium dimethyl;methylene-bis(cyclopentadienyl)zirconium dimethyl;ethylene-bis(cyclopentadienyl)zirconium dimethyl;isopropylidene-bis(cyclopentadienyl)zirconium dimethyl;dimethylsilyl-bis(cyclopentadienyl)zirconium dimethyl;methylene-bis(cyclopentadienyl)zirconium dihydride;ethylene-bis(cyclopentadienyl)zirconium dihydride;isopropylidene-bis(cyclopentadienyl)zirconium dihydride;dimethylsilyl-bis(cyclopentadienyl)zirconium dihydride;(Pentamethylcyclopentadienyl)zirconium trimethyl;(Pentamethylcyclopentadienyl)zirconium triphenyl;(Pentamethylcyclopentadienyl)zirconium tribenzyl;(Pentamethylcyclopentadienyl)zirconium trimethyl;(Cyclopentadienyl)zirconium trimethyl; (Cyclopentadienyl)zirconiumtriphenyl; (Cyclopentadienyl)zirconium tribenzyl;(Cyclopentadienyl)zirconium trimethyl; (Methylcyclopentadienyl)zirconiumtrimethyl; (Methylcyclopentadienyl)zirconium triphenyl;(Methylcyclopentadienyl)zirconium tribenzyl;(Methylcyclopentadienyl)zirconium trimethyl;(Dimethylcyclopentadienyl)zirconium trimethyl;(Trimethylcyclopentadienyl)zirconium trimethyl;(Trimethylsilylcyclopentadienyl)zirconium trimethyl;(Tetramethylcyclopentadienyl)zirconium trimethyl; Indenylzirconiumtrimethyl; Fluorenylzirconium trimethyl; Bis(cyclopentadienyl)zirconiumdimethyl; Bis(cyclopentadienyl)zirconium diphenyl;Bis(cyclopentadienyl)zirconium dibenzyl; Bis(cyclopentadienyl)zirconiumdimethyl; Bis(cyclopentadienyl)zirconium diethyl;Bis(cyclopentadienyl)zirconium dihydride; Bis(cyclopentadienyl)zirconiumdichlorohydride; Bis(methylcyclopentadienyl)zirconium dimethyl;Bis(methylcyclopentadienyl)zirconium diphenyl;Bis(methylcyclopentadienyl)zirconium dibenzyl;Bis(methylcyclopentadienyl)zirconium dimethyl;Bis(pentamethylcyclopentadienyl)zirconium dimethyl;Bis(pentamethylcyclopentadienyl)zirconium dimethyl;Bis(pentamethylcyclopentadienyl)zirconium dibenzyl;Bis(pentamethylcyclopentadienyl)zirconium methylmethyl;Bis(pentamethylcyclopentadienyl)zirconium methylhydride;Ethylenebis(indenyl)zirconium dimethyl; Ethylenebis(indenyl)zirconiumdimethyl; Ethylenebis(tetrahydroindenyl)zirconium dimethyl;Ethylenebis(tetrahydroindenyl)zirconium dimethyl;Dimethylsilylenebis(cyclopentadienyl)zirconium dimethyl;Dimethylsilylenebis(cyclopentadienyl)zirconium dimethyl;Isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Phenylmethylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Ethylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Cyclohyxylidene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Cyclopentylidene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Cyclobutylidene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Dimethylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium dimethyl;Dimethylsilylenebis-(2,3,5-trimethylcyclopentadienyl)zirconium dimethyl;Dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)zirconium dimethyl;Dimethylsilylenebis(indenyl)zirconium dimethyl; Zirconium tetramethyl;Zirconium tetrabenzyl; Zirconium tetramethyl; Zirconium tetramethyl;Zirconium butoxytrimethyl; Zirconium dibutoxydimethyl;Bis(2,5-di-t-butylphenoxy)zirconium dimethyl;Bis(2,5-di-t-butylphenoxy)zirconium dimethyl; Zirconiumbis(acetylacetonate)dimethyl;dimethylsilyl(tetramethylclopentadienyl)cycldodecyloamido)titaniumdimethyl;dimethylsilyl(tetra-methyleyclo-pentadienyl)(1-adamantylamido)titaniumdimethyl;dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titaniumdimethyl; cyclopentadienylzirconium trimethyl; cyclopentadienylzirconiumtriethyl; cyclopentadienylzirconium tripropyl; cyclopentadienyltitaniumtrimethyl; cyclopentadienyltitanium triphenyl; cyclopentadienylscandiumbis(p-tolyl); cyclopentadienylchromium 2,4-pentadienyl;(pentamethylcyclopentadienyl)yttrium bis(bistrimethylsilylmethyl);(pentamethylcyclopentadienyl)scandium bis(bistrimethylsilylmethyl);pentamethylcyclopentadienyl lanthanum bis(bistrimethylsilylmethyl);[1,1′-dimethylsilanylene-bis(2-methyl-indenyl)] hafnium dimethyl;[1,1′-dimethylsilanylene-bis(2-methy-4-phenyl-lindenyl)] hafniumdimethyl; [1,1′-dimethylsilanylene-bis(2-methy-4-naphth-2-yl-lindenyl)]hafnium dimethyl; diphenylmethylene (cyclopentadienyl)(fluorenyl)hafniumdimethyl; [(4-n-butylphenyl)(4-t-butylphenyl)methylene](cyclopentadienyl)(fluorenyl)hafnium dimethyl; dimethylsilanylene(tetramethylcyclopentadienyl)(N-adamantylamido)titanium dimethyl;dimethylsilanylene (tetramethylcyclopentadienyl)(N-t-butylamido)titaniumdimethyl; bis(4-[triethylsilyl])methylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl;bis(4-[triethylsilyl])methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl.

[0071] Additional compounds suitable as olefin polymerization catalystsfor use in this invention will be any of those Group-3-10 compounds thatcan be converted by ligand abstraction or bond scission into a cationiccatalyst and stabilized in that state by a noncoordinating or weaklycoordinating anion sufficiently labile to be displaced by anolefinically unsaturated molecules such as ethylene.

[0072] Exemplary compounds include those described in the patentliterature. International patent publications WO 96/23010, WO 97/48735and Gibson, et al., Chem. Comm., pp. 849-850 (1998), which disclosediimine-based ligands for Group-8 to -10 compounds that undergo ionicactivation and polymerize olefins. Polymerization catalyst systems fromGroup-5-10 metals, in which the active center is highly oxidized andstabilized by low-coordination-number, polyanionic, ligand systems, aredescribed in U.S. Pat. No. 5,502,124 and its divisional U.S. Pat. No.5,504,049. See also the Group-5 organometallic catalyst compounds ofU.S. Pat. No. 5,851,945 and the tridentate-ligand-containing,Group-5-10, organometallic catalysts of copending U.S. application Ser.No. 09/302,243, filed 29 Apr. 1999, and its equivalent PCT/US99/09306.Group-11 catalyst precursor compounds, activable with ionizingcocatalysts, useful for olefin and vinylic polar molecules are describedand exemplified in WO 99/30822 and its priority documents, includingU.S. patent application Ser. No. 08/991,160, filed 16 Dec. 1997.

[0073] U.S. Pat. No. 5,318,935 describes bridged and unbridged, bisamidocatalyst compounds of Group-4 metals capable of a-olefinspolymerization. Bridged bis(arylamido) Group-4 compounds for olefinpolymerization are described by D. H. McConville, et al., inOrganometallics 1995, 14, 5478-5480. Synthetic methods and compoundcharacterization are presented. Further work appearing in D. H.McConville, et al, Macromolecules 1996, 29, 5241-5243, describes bridgedbis(arylamido) Group-4 compounds that are polymerization catalysts for1-hexene. Additional invention-suitable transition metal compoundsinclude those described in WO 96/40805. Cationic Group-3- orLanthanide-metal olefin polymerization complexes are disclosed incopending U.S. application Ser. No. 09/408,050, filed 29 Sep. 1999, andits equivalent PCT/US99/22690. A monoanionic bidentate ligand and twomonoanionic ligands stabilize those catalyst precursors, which can beactivated with this invention's ionic cocatalysts.

[0074] The literature contains many additional descriptions of suitablecatalyst-precursor compounds. Compounds that contain abstractableligands or that can be alkylated to contain abstractable ligands aresuitable for the practice of this invention. See, for instance, V. C.Gibson, et al; “The Search for New-Generation Olefin PolymerizationCatalysts: Life Beyond Metallocenes”, Angew. Chem. Int. Ed., 38, 428-447(1999).

[0075] When using the above catalysts, the catalyst system willgenerally employ one or more scavenging agents to remove polarimpurities from the reaction environment and to increase catalystactivity. Any polymerization reaction components, particularly solvents,monomers, and catalyst feedstreams, can inadvertently introduceimpurities and adversely affect catalyst activity and stability.Impurities decrease or even eliminate catalytic activity, particularlywith ionizing-anion-activated catalyst systems. Polar impurities, orcatalyst poisons, include water, oxygen, metal impurities, etc. Theseimpurities can be removed from or reduced in the reaction componentsbefore their addition to the reaction vessel. Impurities can be removedby chemically treating the components or by impurity separation steps.Such treatment or separation can occur during or after synthesis of thecomponents. In any case, the polymerization process will normally employminor amounts of scavenging agent. Typically, these scavengers will beorganometallic such as the Group-13 compounds of U.S. Pat. Nos.5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132,and that of WO 95/07941. Exemplary compounds include triethyl aluminum,triethyl borane, triisobutyl aluminum, methylalumoxane, and isobutylalumoxane. Those compounds having bulky or C₆-C₂₀ linear hydrocarbylsubstituents connected to the metal or metalloid center are preferredbecause they coordinate to the active catalyst more weakly. Examplesinclude triethylaluminum and bulky compounds such astriisobutylaluminum, triisoprenylaluminum, and long-chain,linear-alkyl-substituted aluminum compounds, such astri-n-hexylaluminum, tri-n-octylaluminum, or tri-n-dodecylaluminum. Whenalumoxane is used as activator, any excess over that needed to activatethe catalyst can act as a scavenger and additional organometallicscavengers may be unnecessary. Alumoxanes also may be used as scavengerswith other activators, e.g., methylalumoxane and triisobutyl-alumoxanewith boron-based activators. The scavenger amount is limited to thatamount effective to enhance activity (and with that amount necessary foractivation when used in a dual role) since excess amounts may act ascatalyst poisons.

[0076] This invention's catalyst systems can polymerize thoseunsaturated molecules conventionally recognized as polymerizable usingmetallocenes. Typical conditions include solution, slurry, gas-phase,and high-pressure polymerization. The catalysts may be supported oninorganic oxide or polymeric supports and as such will be particularlyuseful in those operating modes employing fixed-bed, moving-bed,fluid-bed, slurry, or solution processes conducted in single, series, orparallel reactors. Invention cocatalysts may also function in catalystpre-polymerization. WO 98/55518, describes a support method forgas-phase or slurry polymerization.

[0077] Alternative invention embodiments employ the catalyst system inliquid phase (solution, slurry, suspension, bulk phase, or combinationsthereof), in high-pressure liquid or supercritical fluid phase, or ingas phase. These processes may also be employed in singular, parallel,or series reactors. The liquid phase processes comprise contactingolefin molecules with the catalyst system described above in a suitablediluent or solvent and allowing those molecules to react long enough toproduce the invention polymers. The term polymer encompasses both homo-and co-polymers. Both aliphatic and aromatic hydrocarbyl solvents aresuitable; some embodiments select hexane. In bulk and slurry processes,the supported catalysts typically contact a liquid monomer slurry.Gas-phase processes use a supported catalyst and follow any mannersuitable for ethylene polymerization, although, some embodiments selectthe maximum pressure to be as low as 1600 or 500. Illustrative examplesmay be found in U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,382,638, 5352,749, 5,408,017, 5,436,304, 5,453,471, and 5,463,999,5,767,208 and WO 95/07942.

[0078] The minimum, polymerization reaction temperature is 40° C. Someembodiments select the minimum reaction temperature to be 60° C. Thetemperature can go as high as 250° C., but some embodiments choose notto exceed 220° C. The minimum reaction pressure is 0.001 bar; although,some embodiments choose the minimum pressure to be as high as 0.1 or 1.0bar. The maximum pressure is less than or equal to 2500 bar.

[0079] Invention catalyst systems can produce various polyethylenesincluding high- and ultra-high-molecular weight polyethylenes. Thesepolyethylenes can be either homopolymers or copolymers with otherα-olefins or α-olefinic or non-conjugated diolefins, e.g. C₃-C₂₀olefins, diolefins, or cyclic olefins. In some embodiments, a lowpressure (typically <50 bar) vessel is used. Invention activatedcatalysts are slurried with a solvent (typically hexane or toluene). Thepolyethylenes are produced by adding ethylene, and optionally one ormore other monomers, along with the slurried catalyst to the lowpressure vessel. The temperature is usually within the 40-250° C. range.Cooling removes polymerization heat. Gas-phase polymerization can beconducted, for example, in a continuous fluid-bed, gas-phase reactoroperated at a minimum of 2000 kPa and up to 3000 kPa. The minimumtemperature is 60° C.; the maximum temperature is 160° C. The gas-phasereaction uses hydrogen as a reaction modifier at a concentration of noless than 100 PPM. The hydrogen gas concentration should not exceed 200PPM. The reaction employs a C₄-C₈ comonomer feedstream and a C₂feedstream. The C₄-C₈ feedstream goes down to 0.5 mol %. It also may goup to 1.2 mol %. Finally, the C₂ feedstream has a minimum concentrationof 25 mol %. Its maximum concentration is 35 mol %. See, U.S. Pat. Nos.4,543,399, 4,588,790, 5,028,670 and 5,405,922 and 5,462,999.

[0080] High-molecular-weight, low-crystallinity, ethylene-α-olefinelastomers (including ethylene-cyclic-olefin andethylene-α-olefin-diolefin elastomers) can be prepared using inventioncatalyst systems under traditional solution processes or by introducingethylene into invention catalyst slurries with α-olefin, cyclic olefin,or either or both mixed with other polymerizable and non-polymerizablediluents. Typical ethylene pressures range from 10 to 1000 psig (69-6895kPa) and the diluent temperature typically remains between 40 and 160°C. The process can occur in one or more stirred tank reactors, operatedindividually, in series, or in parallel. The general disclosure of U.S.Pat. No. 5,001,205 illustrates general process conditions. See also,international application WO 96/33227 and WO 97/22639.

[0081] Besides those specifically described above, other molecules maybe polymerized using invention catalyst systems, for example, styrene,alkyl-substituted styrenes, isobutylene and other geminallydisubstituted olefins, ethylidene norbornene, norbornadiene,dicyclopentadiene, and other olefinically-unsaturated molecules,including other cyclic olefins, such as cyclopentene, norbornene,alkyl-substituted norbornenes, and vinylic polar, polymerizablemolecules. See, for example, U.S. Pat. Nos. 5,635,573, 5,763,556, and WO99/30822. Additionally, α-olefin macromers of up to 1000 mer units ormore may be copolymerized yielding branched olefin polymers.Additionally, activated cation catalysts for oligomerization,dimerization, hydrogenation, olefin/carbon-monoxide copolymerization,hydroformulation, hydrosilation, hydroamination, and related reactionscan be activated with invention cocatalysts.

[0082] The invention cocatalysts can activate individual catalysts orcan activate catalysts mixtures for polymer blends. Adept monomer andcatalyst selection yields polymer blends analogous to those usingindividual catalyst compositions. Polymers having increased MWD (forimproved processing) and other benefits available frommixed-catalyst-system polymers can be achieved using inventioncocatalysts.

[0083] Blended polymer formation can be achieved ex situ throughmechanical blending or in situ through using mixed catalyst systems. Itis generally believed that in situ blending provides a more homogeneousproduct and allows the blend to be produced in one step. In-situblending with mixed catalyst systems involves combining more than onecatalyst in the same reactor to simultaneously produce multiple,distinct polymer products. This method requires additional catalystsynthesis, and the various catalyst components must be matched for theiractivities, the polymer products they generate at specific conditions,and their response to changes in polymerization conditions. Inventioncocatalysts can activate mixed catalyst systems.

EXAMPLES

[0084] The following examples are presented to illustrate the foregoingdiscussion. All parts, proportions, and percentages are by weight unlessotherwise indicated. Where necessary, the examples were carried out indry, oxygen-free environments and solvents. Although the examples may bedirected to certain embodiments of the present invention, they do notlimit the invention in any specific respect. Certain abbreviations areused to facilitate the description. These include standard chemicalabbreviations for the elements and certain commonly acceptedabbreviations, such as: Me=methyl, Et=ethyl, n-Pr=normal-propyl,t-Bu=tertiary-butyl, Ph=phenyl, pfp=pentafluorophenyl,Cp=cyclopentadienyl, Ind=indenyl, Flu=fluorenyl, TMS=trimethylsilyl,TES=triethylsilyl and THF (or thf)=tetrahydrofuran.

[0085] All molecular weights are weight average molecular weight unlessotherwise noted. Molecular weights (weight average molecular weight(Mw)) and number average molecular weight (Mn) were measured by GelPermeation Chromatography (GPC) using a Waters 150 Gel PermeationChromatograph equipped with a differential refractive index (DRI) andlow angle light scattering (LS) detectors. The GPC instrument wascalibrated using polystyrene standards. Samples were run in1,2,4-trichlorobenzene (135° C.) using three Polymer Laboratories PC Gelmixed B columns in series. This general technique is discussed in“Liquid Chromatography of Polymers and Related Materials III′” J. CazesEd., Marcel Decker, 1981, page 207, which is incorporated by referencefor purposes of U.S. patent practice. No corrections for columnspreading were employed; but data on generally accepted standards, e.g.National Bureau of Standards Polyethylene 1475, demonstrated a precisionwith 0.2 units for Mw/Mn as calculated from elution times.

EXAMPLES Example 1

[0086] Synthesis of HC₆F₄-CC-Si(i-Pr)₃: Sonogashira methodology wasemployed for the coupling reaction. To 150 milliliters of triethylaminewas added Pd(OAc)₂ (0.733 grams), P(C₆H₅)₃ (2.55 grams), and CuI (0.880grams). HC₅F₄Br (17.00 grams) was added to the mixture, followed byHCCTMS (15.00 grams). After 15 minutes of completing the additions, themixture turned dark and precipitate was observed. After stirring at roomtemperature for 20 minutes, the reaction was refluxed for 20 hours. Thesolids were filtered off. The filtrate were taken up with 300milliliters of diethylether and washed with 5% HCl (aq). The organiclayer were separated and dried with MgSO₄. After the required amount oftime the drying agent was removed and the solvent volume reduced. Columnchromatography removes most of the dark colored impurities. Distillationaffords the final product (oil bath at 125 deg C., bp=98 deg C. at 10⁻⁴milli-torr) as a colorless product (9.80 grams). ¹H NMR (CDCl₃, 25 degC.): 7.03 (m, 1H), 1.11 (bs, 21H).

Example 2

[0087] Synthesis of [Li(Et₂O)_(2.5)][B(C₆F₄-CC-Si(i-Pr)₃)₄]: To a coldsolution of HC₆F₄-CC-Si(i-Pr)₃ in diethylether was added BuLi (10milliliters, 1.6 M, Aldrich). After 5 minutes the solution turned a palegreen. The reaction was allowed to stir at −78 deg C. for 1 hour. BCl₃(4.0 milliliter, 1.0 M, Aldrich) was added. The reaction was stirred for4 hours. The solvent was replaced with methylene chloride and the LiClremoved by filtration. The solvent was reduced and pentane was added toincipient cloudiness. The mixture was chilled overnight and theresulting white crystalline product collected by filtration (2.305grams). ¹H NMR (Tol_(-d8), 25 deg C.): 3.10 (q, 12H), 1.14 (m, 84)

Example 3

[0088] Synthesis of [DMAH][B(C₆F₄-CC-Si(i-Pr)₃)₄]: To a methylenechloride solution of [Li(Et₂O)_(2.5)][B(C₆F₄-CC-Si(i-Pr)₃)₄] (2.281grams) was added a solution of DMAHCl (0.236 grams). The resulting LiClwas removed by filtration after stirring for 1 hour. The solvent volumewas reduced and the product precipitated out with pentane. The resultingproduct is a white solid (1.851 grams). ¹H NMR (CD₂Cl₂, 25 deg C.): 7.63(m, 3H), 7.29 (m, 2H), 3.35 (s, 6H), 1.10 (bs, 84H). ¹⁹F NMR (CD₂Cl₂, 25deg C.): −133.1, −141.4.

Example 4

[0089] Polymerization reactions: The polymerization reaction ofpropylene were carried out in a ½ liter, autoclave batch reactoroperating at 60° C. The catalyst used was bis(indenyl)dimethylsilylhafnium dimethyl. In all cases the polymerization solvent was hexanes,while the activation solvent was toluene. Standard runs using[B(C₆F₅)₄][C₆H₅NMe₂H] as the activating cocatalyst were carried out.Trioctylaluminium was used as the scavenger in all runs (25% wt). Thescavenger-catalyst mole ratios for these two reactions were less than10. The polymers were precipitated with isopropyl alcohol and dried in avacuum oven at 75° C. To constant weights. The polymer melting pointswere determine with DSC, while the molecular weights were measured byGPC. Results of Propylene Polymerization Reactions Catalyst MeltingPoint System Mw (GPC) Mn (GPC) Polymer Yield (g) (° C.) A/B 305,862176,510 5.6 139 A/B 250,514 133,629 13.3 139 A/B 323,947 121,767 23.5139 A/B 754,694 171,150 6.4 141 A/B 722,561 153,870 11.7 140 A/C 224,404118,690 NA 137 A/C 306,886 120,972 27.0 137

[0090] While certain representative embodiments and details have beenshown to illustrate the invention, it will be apparent to skilledartisans that various process and product changes from those disclosedin this application may be made without departing from this invention'sscope, which the appended claims define.

[0091] All cited patents, test procedures, priority documents, and othercited documents are fully incorporated by reference to the extent thatthis material is consistent with this specification and for alljurisdictions in which such incorporation is permitted.

[0092] Certain features of the present invention are described in termsof a set of numerical upper limits and a set of numerical lower limits.This specification discloses all ranges formed by any combination ofthese limits. All combinations of these limits are within the scope ofthe invention unless otherwise indicated.

50. A composition of matter comprising a Group-13 atom connected to fouraryl ligands wherein at least one aryl is substituted with an acetylenegroup.
 51. The composition of matter of claim 50 wherein at least onearyl ligand is selected from phenyl, indenyl, naphthyl, fluorenyl, orpyrenyl.
 52. The composition of matter of claim 51 wherein all of thearyl ligands are the same.
 53. The composition of matter of claim 50wherein the Group-13 atom is boron.
 54. The composition of matter ofclaim 50 wherein the acetylene moiety is substituted with an alkynefunctional group connected to a bulky ligand.
 55. The composition ofmatter of claim 50 wherein the acetylene moiety is represented by thefollowing structure:

wherein the filled circle represents a bulky group.
 56. The compositionof matter of claim 50 wherein the acetylene moiety is represented by thefollowing formula:

wherein (a) R are the same or different organic radicals; and (b) Si issilicon.
 57. The composition of matter of claim 56 wherein R is selectedfrom substituted or unsubstituted propyl, isopropyl, butyl, isobutyl,tertiary butyl, pentyl, isopentyl, and cyclohexyl.
 58. The compositionof matter of claim 50 wherein at least one acetylene moiety is atriispropylsilyl radical.
 59. The composition of matter of claim 50further comprising a cation.
 60. An activator comprising the compositionof matter of claim 59 wherein the cation is an activating cation. 61.The activator of claim 60 wherein the cation is one of anilinium,ammonium, trityl carbenium, Group-11 metal, silylium, hydrated Group-1or -2 metal salt cations.
 62. A composition of matter comprising aGroup-13 atom connected to three aryl ligands wherein (a) at least onearyl ligand is substituted with at least one fluorine atom connected toa ring carbon atom and (b) at least one aryl ligand is substituted withan acetylene moiety.
 63. The composition of matter of claim 62 whereinat least one aryl ligand is selected from phenyl, indenyl, naphthyl,fluorenyl, or pyrenyl.
 64. The composition of matter of claim 63 whereinall of the aryl ligands are the same.
 65. The composition of matter ofclaim 62 wherein the Group-13 atom is boron.
 66. The composition ofmatter of claim 62 wherein the acetylene moiety is substituted with analkyne functional group connected to a bulky ligand.
 67. The compositionof matter of claim 62 wherein the acetylene moiety is represented by thefollowing structure:

wherein the filled circle represents a bulky group.
 68. The compositionof matter of claim 62 wherein the acetylene moiety is represented by thefollowing formula:

wherein (a) R are the same or different organic radicals; and (b) Si issilicon.
 69. The composition of matter of claim 68 wherein R is selectedfrom substituted or unsubstituted propyl, isopropyl, butyl, isobutyl,tertiary butyl, pentyl, isopentyl, and cyclohexyl.
 70. The compositionof claim 62 wherein at least one acetylenic moiety is a triispropylsilylradical.
 71. A catalyst system comprising the composition of claim 62and a transition metal catalyst precursor.
 72. An olefin polymerizationprocess comprising: (a) contacting a composition comprising a Group-13atom connected to four aryl ligands wherein at least one aryl issubstituted with an acetylene group with at least one catalystprecursor(s) thereby forming activated catalyst(s) and non-coordinatinganion(s); and (b) contacting the activated catalyst(s) with olefinmonomer(s) thereby causing olefin polymerization.
 73. A compositionrepresented by one of the following:

wherein (a) R^(a) and R^(b) are independently selected from hydrogen,C₁-C₃₀ hydrocarbyls, fluorine, or —C≡C- wherein the filled circlerepresents a bulky group and wherein R are the same or different organicradicals, provided that at least one of R^(a) or R^(b) is selected from—C≡C-.
 74. The composition of claim 73 wherein (a) at least one R^(b)is —C≡C- wherein the filled circle represents a bulky group and theremaining R^(b) are independently selected from from hydrogen, C₁-C₃₀hydrocarbyls, fluorine, or —C≡C-; and (b) R^(a) are independentlyselected from hydrogen, C₁-C₃₀ hydrocarbyls, or fluorine.
 75. Thecomposition of claim 73 wherein (a) for each aryl ligand at least oneR^(b) is —C≡C- and the remaining R^(b) are independently selected fromfrom hydrogen, C₁-C₃₀ hydrocarbyls, fluorine, or —C≡C-; and (b) R^(a)are independently selected from hydrogen, C₁-C₃₀ hydrocarbyls, orfluorine.
 76. The composition of claim 73 wherein all aryl ligands arethe same.
 77. A composition having the following formula:

where iPr is isopropyl.
 78. A composition having the following formula:

where iPr is isopropyl.
 79. A composition represented by one of thefollowing:

wherein (a) R^(a) and R^(b) are independently selected from hydrogen,C₁-C₃₀ hydrocarbyls, fluorine, or —C≡C- wherein the filled circlerepresents a bulky group and R are the same or different organicradicals, provided that at least one of R^(a) or R^(b) is selected from—C≡C- and provided that one of the remaining R^(a) or R^(b) is fluorineor a fluroine-substituted hydrocarbyl.
 80. The composition of claim 79wherein (a) at least one R^(b) is —C≡C- and the remaining R^(b) areindependently selected from from hydrogen, C₁-C₃₀ hydrocarbyls,fluorine, or —C≡C-; and (b) R^(a) are independently selected fromhydrogen, C₁-C₃₀ hydrocarbyls, or fluorine.
 81. The composition of claim79 wherein (a) for each aryl ligand at least one R^(b) is —C≡C- and theremaining R^(b) are independently selected from from hydrogen, C₁-C₃₀hydrocarbyls, fluorine, or —C≡C-; and (b) R^(a) are independentlyselected from hydrogen, C₁-C₃₀ hydrocarbyls, or fluorine.
 82. Thecomposition of claim 79 wherein all aryl ligands are the same.